Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
  • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
• • C—CHEMISTRY; METALLURGY
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6245—Polymers having terminal groups containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
  • C08G18/8077—Oximes
• • C—CHEMISTRY; METALLURGY
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
  • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• • D—TEXTILES; PAPER
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  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/02—Natural fibres, other than mineral fibres
  • D06M2101/04—Vegetal fibres
  • D06M2101/06—Vegetal fibres cellulosic
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/32—Polyesters

Definitions

• the present invention relates to fluorochemical compositions for the treatment of substrates, in particular fibrous substrates such as textiles to impart stain release properties to those substrates.
• Fluorochemical compositions for the treatment of substrates such as leather, textiles and paper, are well known and are used to impart various properties to the substrate such as water and/or oil repellency, waterproofhess, anti-staining, and soil-resistance.
• substrates such as leather, textiles and paper
• properties such as water and/or oil repellency, waterproofhess, anti-staining, and soil-resistance.
• 5,100,954 discloses a soil resisting agent containing, as an effective component, a copolymer of (I) a fluorine- containing urethane compound containing a (meth)acryloyl group or an allyl group, and a polyfluoroalkyl group, obtained by reacting (a) a polyfunctional isocyanate having at least trifunctionality, (b) a hydroxy compound containing a (meth)acryloyl group or an allyl group, and (c) a hydroxy compound having a polyfluoroalkyl group, and (II) a copolymerizable compound other than said fluorine-containing urethane compound.
• a copolymer of (I) a fluorine- containing urethane compound containing a (meth)acryloyl group or an allyl group, and a polyfluoroalkyl group obtained by reacting (a) a polyfunctional isocyanate having at least trifunctionality, (
• U.S. Patent No. 4,920,190 describes certain fluorochemical compositions that are based on polymers of fluorinated acrylic monomers in which a perfluoroalkyl group is linked by 2,4-toluenediisocyanate to an acrylate or methacrylate.
• acrylates and methacrylates are mentioned mono- (meth)acrylates of polyalkyleneglycols.
• the fluorochemical compositions are said to be suitable as water or oil-repellents for various substrates and in particular leather.
• 4,778,915 describes certain polymers of fluorinated acrylic monomers that contain a perfluoroalkyl group linked to an acrylate or methacrylate by a di-isocyanate, for use as water or oil repellents.
• Fluorochemical compositions are also used to facilitate stain or soil release from a substrate such as, for example, a fabric.
• Routine treatments of fabrics with various modifying additives such as softeners, stiffeners, and lubricants, to impart desired properties to a commercial fabric typically increase the oleophilicity of the fabric, thereby significantly increasing its tendency to accept oily stains and reducing its ability to release such stains after laundering.
• Fluorochemical compositions based on a mixture of a fluorinated compound and a non-fluorinated hydrophilic compound or a chemical "hybrid” compound containing fluorochemical oleophobic segments (“F") and non-fluorinated hydrophilic segments (“H”) are known to act as stain release compositions since they provide oil repellency during normal wear and inhibit wicking or diffusion of oily soils into the fabric or fiber bundles as well as facilitate soil release during laundering.
• U.S. Patent No. 4,859,754 describes certain water and oil repellent treatments having desoiling properties that are composed of a polyfluorinated group containing copolymer obtained by copolymerizing a first and second monomer wherein the first monomer contains a polyfluorinated group and the second monomer is an amphiphatic monomer having a hydrophilic moiety and a lipophilic moiety.
• U.S. Patent No. 3,920,614 describes certain high soil release oil-and water repellent copolymers prepared by copolymerization of at least 25% by weight of a fluoroalkyl monomer and 5 to 50% by weight of poly(oxyethylene) acrylate or methacrylate.
• U.S. Patent No. 4,695,488 describes certain polymers obtained by homopolymerization of poly(oxyalkylene) monomers terminated by fluorinated groups. According to the disclosure, a composition based on this polymer could impart stainproofing properties with good durability to a substrate such as plastics, fabric and paper.
• Desirable properties include easy cleanability of substrates based on natural fibers such as cotton and blends of cotton and polyester, particularly with respect to oil type stains (dirty motor oil, vegetable oil) and water based stains (tea, coffee, wine); low manufacturing cost; high storage stability; easy emulsifiability and high performance even if applied in low quantities. It is also desired that the fluorochemical compositions provide good stain release properties and oil and/or water repellency properties to the substrate.
• the present invention provides a method of treatment of a substrate comprising the step of contacting said substrate with a fluorochemical composition comprising a polymer derived from polymerization of monomer corresponding to the following general formula (I): (RrO ⁇ - 3
• R f is selected from the group consisting of perfluorinated or partially fluorinated aliphatic groups; L 1 and L 2 are each independently an organic divalent linking group and they may be the same or different;
• L 3 represents an organic linking group with a valence of n + 1; t is O or 1; n is an integer of 2 to 20; A 1 and A 2 are each independently selected from the group consisting of divalent residues obtained by removing 2 -NCO groups from a corresponding diisocyanate;
• X 1 is selected from the group consisting of O, NH and S;
• X 2 is selected from the group consisting of O, NH and S;
• B 1 represents a hydrophilic residue obtained by removing the groups HX 1 and HX 2 from a compound HX 1 -B 1 -X 2 H that comprises a poly(oxyalkylene) group;
• G represents a free radical polymerizable group; and s is 0 or 1 with the proviso that when s is 0, L 2 represents a hydrophilic segment comprising a poly(oxyalkylene) group or said polymer is derived from a copolymerization of a monomer according to formula (I) and a poly(oxyalkylene) group containing monomer.
• a fluorochemical composition comprising a polymer derived from a polymerization of a monomer corresponding to the following general formula (I):
• R f is selected from the group consisting of perfluorinated or partially fluorinated aliphatic groups
• L 1 and L 2 are each independently selected from the group consisting of organic divalent linking groups;
• L 3 is an organic linking group with a valence of n + 1; t is 0 or 1; n is an integer of 2 to 20;
• a 1 and A 2 are each independently selected from the group consisting of divalent residues obtained by removing twp -NCO groups from a corresponding diisocyanate;
• X 1 is selected from the group consisting of O, NH and S;
• X 2 is selected from the group consisting of O, NH and S;
• B 1 represents a hydrophilic segment comprising a poly(oxyalkylene) group
• G represents a free radical polymerizable group
• s is 0 or 1 with the proviso that when s is 0,
• L 2 represents a hydrophilic segment comprising a poly(oxyalkylene) group or said polymer is derived from a copolymerization of a monomer according to formula (I) and a poly(oxyalkylene) group containing monomer.
• a monomer according to formula (I) above and a monomer composition including a monomer according to formula (I) and a poly(oxyalkylene)-containing monomer.
• the polymer used in the fluorochemical composition is derived from at least one monomer according to formula (I) above. If the monomer according to formula (I) includes a poly(oxyalkylene) group, i.e. s is 1, and/or L 2 contains a polyoxyalkylene a homopolymer of the monomer of formula (I) can be used as well as a copolymer of that monomer.
• the polyoxyalkylene group is typically of a sufficient length such that sufficient wetting of the substrates occurs during laundering thereby facilitating removal of stain.
• the number of oxyalkylene moieties in the poly(oxyalkylene) group is between about 18 and 275 or between about 20 and 190 and more preferably between about 23 and 95.
• the polymer is derived from at least a monomer of formula (I) and at least one comonomer that includes a poly(oxyalkylene) group preferably having between about 5 and 16 oxyalkylene moieties.
• the polymer may further include other ethylenically unsaturated comonomers such as vinylacetate, acrylates and methacrylates (e.g., methyl(meth)acrylate, glycidyl methacrylate, ethyl(meth)acrylate), vinylchloride, vinylidenechlorides, styrenes, acrylic acids, methacrylic acids and acrylonitriles.
• ethylenically unsaturated comonomers such as vinylacetate, acrylates and methacrylates (e.g., methyl(meth)acrylate, glycidyl methacrylate, ethyl(meth)acrylate), vinylchloride, vinylidenechlorides, styrenes, acrylic acids, methacrylic acids and acrylonitriles.
• Suitable comonomers include urethane-acrylate or urethane-methacrylate type monomers that can be obtained by the reaction of a diisocyanate and a hydroxy or amino-functionalised acrylate or methacrylate and another hydroxy or amino- functionalised compound such as an isocyanate blocking agent.
• Particular examples of the latter type of comonomers include the reaction product of a diisocyanate, 2- hydroxyethyl(meth)acrylate and 2-butanone oxime or the reaction product of a diisocyanate, a mono (meth)acrylate of a polyethylene glycol and 2-butanone oxime.
• the polymer includes between about 25% and 100% based on the total number of units in the polymer, preferably between about 40% and 100% of units derived from a monomer according to formula (I) that contains a poly(oxyalkylene) group.
• the polymer is derived from monomers according to formula (I) that do not include the poly(oxyalkylene) group
• the polymer also includes a comonomer that contains poly(oxyalkylene) groups.
• the number of moieties in the polymer derived from monomers according to formula (I) not including poly(oxyalkylene) is preferably between about 5% and 50%, more preferably between about 15% and 40% and the number of units derived from a poly(oxyalkylene) containing comonomer is preferably between about 50% and 95% and more preferably between about 60% and 85%.
• the fluorinated aliphatic group, Rf is preferably a fluorinated, stable, inert, preferably saturated, non-polar, monovalent alkyl group. It can be straight chain, branched chain, or cyclic or combinations thereof. It can contain heteroatoms, bonded only to carbon atoms, such as oxygen, divalent or hexavalent sulfur, or nitrogen.
• Rf is preferably a fully-fluorinated alkyl group, but hydrogen or chlorine atoms can be present as substituents, but preferably not more than one atom of either is present for every two carbon atoms.
• the Rf group typically has at least about 3 carbon atoms, preferably about 3 to 14 carbon atoms and more preferably at least about 6 carbon atoms.
• Rf preferably contains about 40% to 80% fluorine by weight, more preferably about 50% to 78% fluorine by weight.
• the terminal portion of the Rf radical is preferably a perfluorinated moiety, preferably containing at least about 7 fluorine atoms, e.g., CF 3 CF 2 CF 2 -, (CF 3 ) 2 CF-, F 5 SCF 2 -.
• Preferred R f groups are fully or substantially fluorinated and are preferably those perfluorinated alkyls according to the formula m is 3 to 14.
• a monomer according to formula (I) includes a plurality of Rf groups as indicated by the variable n. Preferably, the monomer contains 3 to 6 or more R f groups.
• linking groups L 1 include straight chain, branched chain or cyclic alkylene, arylene, aralkylene, oxy, oxo, thio, sulfonyl, sulfoxy, amino, imino, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene groups, and combinations thereof such as sulfonamidoalkylene or carbonamidoalkylene.
• a particularly preferred linking group L 1 is represented by one of the following formulas: -SO 2 N-R 3 -OOC- ; -R 3 -OOC- ; -R 3 -NHCO-
• R 3 is selected from the group consisting of linear or branched alkylenes having 2 to 4 carbon atoms, and
• R 4 represents an alkyl having about 1 to 4 carbon atoms, for example methyl, ethyl or n-butyl.
• L 3 is a linking group with a valence of n + 1 that preferably corresponds to the following formula:
• n is as defined above,
• Z represents the residue of a free radical initiator
• R 5 is hydrogen or a methyl group
• X 5 is S, X° is O or NH and
• L 5 represents an alkylene preferably having 2 to 4 carbon atoms.
• B 1 is the hydrophilic residue obtained by removing the groups HX 1 and HX 2 from a compound HX 1 -B 1 -X 2 H that comprises a poly(oxyalkylene) group.
• Suitable poly(oxyalkylene)groups include those of which the oxyalkylene moiety has 2 to 4 carbons such as -OCH 2 -CH 2 -, -OCH 2 -CH 2 -CH 2 -, -OCH(CH 3 )CH 2 -, and -OCH(CH 3 )CH(CH 3 )-.
• the oxyalkylene moieties in the poly(oxyalkylene) group can be the same, as in poly(oxypropylene), or can be present as a mixture, as in a heteric straight or branched chain polymer or polymer with randomly distributed oxyethylene and oxypropylene moieties, or as in a straight or branched chain polymer with blocks of oxyethylene units and blocks of oxypropylene units.
• the poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages. Where the catenary linkages have three or more valences, they provide a means for obtaining a branched chain of oxyalkylene moieties.
• the poly(oxyalkylene) group may further contain a mixture of oxyalkylene moieties such as a mixture of oxyethylene and oxypropylene.
• the majority of oxyalkylene moieties are oxyethylene, and preferably the number of oxyethylene moieties is at least about 50% and more preferably at least about 70%.
• the average number of oxyalkylene moieties is typically between about 18 and 275 and more preferably between about 25 and 182.
• B 1 may also include an organic divalent linking group that links the poly(oxyalkylene) group to X 1 or X 2 .
• Such organic divalent linking group is preferably a lower alkylene moiety having between 1 and 4 carbon atoms such as a methylene or ethylene moiety.
• B 1 is the hydrophilic residue obtained by removing the groups HX 1 and HX 2 from a compound HX 1 -B 1 -X 2 H selected from the group consisting of poly(oxyalkylene)diols (such as polyethyleneglycol), poly(oxyalkylene)thiols and poly(oxyalkylene)diamines.
• poly(oxyalkylene)diols such as polyethyleneglycol
• poly(oxyalkylene)thiols such as polyethyleneglycol
• poly(oxyalkylene)diamines such as polyethyleneglycol
• L 2 is an organic divalent linking group such as oxy, amino, linear or branched alkylenes having 1 to 4 carbon atoms or poly(oxyalkylenes) containing a group such as polyethyleneoxide or polypropyleneoxide.
• L 2 preferably comprises a poly(oxyalkylene) group having between about 5 and 20 oxyalkylene groups.
• R 2 wherein: X 3 and X 4 each independently are selected from O or NH,
• R 1 is a linear or branched alkylene having 2 to 4 carbon atoms or a poly(oxyalkylene) containing group
• R 2 is hydrogen or a methyl group
• the monomers according to formula (I) wherein s is 1 are typically prepared according to the following general procedure.
• a first reaction an oligomer containing a plurality of Rf groups and a functionality capable of reacting with an isocyanate is reacted with a diisocyanate.
• the oligomers can be prepared according to the procedure described in, e.g., U.S. Patent No. 5,292,796.
• their preparation involves a free radical polymerisation of a fluorochemical compound having an ethylenic unsaturation in the presence of an end-capping agent that includes a functional group capable of reacting with an isocyanate.
• Fluorochemical compounds having an ethylenic unsaturation are disclosed, e.g., in U.S. Patent Nos. 2,803,615 (Ahlbrecht et al.) and 2,841,573 (Ahlbrecht et al.).
• Examples of such compounds include general classes of fluorochemical olefins such as acrylates, methacrylates, vinyl ethers, and allyl compounds containing fluorinated sulfonamido groups, acrylates or methacrylates derived from fluorochemical telomer alcohols, fluorochemical thiols, and the like.
• comonomers such as acrylates and methacrylates can be used.
• Suitable end-capping agents typically include a mercapto group and a functional group capable of reacting with an isocyanate. Such functional groups include hydroxy and amino.
• Examples of end-capping agents include 2- mercaptoethanol, 11-mercaptoundecanol, 3-mercapto-2-butanol, l-mercapto-2- propanol, 2-mercaptopyridinol, o-, m-, and p-thiocresol and 2-mercaptoethylamine.
• Preferred functionalized end-capping agents include 2-mercaptoethanol, 4- mercaptobutanol and 2-mercaptoethylamine.
• Suitable diisocyanates that can be used include aromatic diisocyanates such as 4,4'-methylenediphenylenediisocyanate, 4, 6-di-(trifluoromethyl)- 1,3 -benzene diisocyanate, 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p- xylylene diisocyanate, 4,4'-diisocyanatodiphenylether, 3,3'-dichloro-4,4'- diisocyanatodiphenylmethane, 4,5'-diphenyldiisocyanate, 4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4
• a diisocyanate which may be the same or different as the one used in the above described reaction, is reacted with a monomer that contains a group capable of reacting with an isocyanate such as hydroxy or amino.
• Preferred monomers are acrylates, methacrylates, acrylamides and methacrylamides. Especially preferred monomers correspond to the following formula:
• X 3 and X 4 are each independently selected from O or NH,
• R 1 is a linear or branched alkylene having 1 to 4 carbon atoms or a poly(oxyalkylene) containing group
• R 2 is hydrogen or a methyl group.
• Specific examples include 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 6-hydroxy-hexyl(meth)acrylate, mono (meth)acrylates of a polyethylene glycol, mono (meth)acrylates of a block copolymer of ethylene oxide and propylene oxide; mono (meth)acrylates of amino- or diamino- terminated polyethers and mono (meth)acrylates of tetramethylene oxide glycols.
• reaction products of the above described first and second reaction can then be combined and reacted with a compound of the formula HX I -B 1 -X 2 H.
• Suitable compounds of the latter formula are described herein.
• the reaction conditions that can be employed in each of these three reactions are the conventional reaction conditions employed in reacting an isocyanate.
• the reactions are run in the presence of a catalyst.
• Suitable catalysts include tin salts such as dibutyltin dilaurate, stannous octanoate, stannous oleate, tin dibutyldi-(2- ethyl hexanoate), stannous chloride; and others known to those skilled in the art.
• catalyst concentrations are from about 0.001 percent to 10 percent, preferably about 0.1 percent to 5 percent, by weight based on the total weight of the reactants.
• condensation reactions are preferably carried out under dry conditions in a polar solvent such as ethyl acetate, acetone, methyl isobutyl ketone, toluene and the like.
• a polar solvent such as ethyl acetate, acetone, methyl isobutyl ketone, toluene and the like.
• Suitable reaction temperatures will be easily determined by those skilled in the art based on the particular reagents, solvents, and catalysts being used. While it is not practical to enumerate particular temperatures suitable for all situations, generally suitable temperatures are between about room temperature and about 120°C.
• Monomers according to formula (I) wherein s is 0 can be prepared in a single step by reacting the fluorochemical oligomer and a monomer that contains a group capable of reacting with an isocyanate such as hydroxy or amino with a diisocyanate. Suitable diisocyanates, monomers containing a group capable of reacting with an isocyanate and the fluorochemical oligomers are described herein. As described herein, where the monomer according to formula (I) does not include a polyoxyalkylene group, the polymer is derived from a copolymerisation of a monomer according to formula (I) and a comonomer containing a poly(oxyalkylene) group.
• the comonomer containing a poly(oxyalkylene) group can be a monomer corresponding to formula (I) with s being 1 or L 2 containing a poly(oxyalkylene) group, but preferably it is a monomer that does not contain a fluorochemical group.
• Preferred comonomers correspond to the following formula:
• R 6 , R 7 and R 8 are each independently selected from the group consisting of linear or branched alkylenes having 2 to 4 carbon atoms;
• R 9 is hydrogen or an alkyl group having 1 to 4 carbon atoms;
• x and y are each independently an integer of 0 to about 30, typically 0 to about 20 and preferably 0 to about 16, and the sum of x and y is at least about 5; and
• R 10 is hydrogen or a methyl group.
• Examples of comonomers containing a poly(oxyalkylene) group include mono (meth)acrylates of a polyethylene glycol, mono (meth)acrylates of a block copolymer of ethylene oxide and propylene oxide; mono (meth)acrylates of amino- or diamino- terminated polyethers and (meth)acrylates of methoxypolyethyleneglycols.
• the polymer of the fluorochemical composition is typically prepared by free radical polymerisation e.g. by solution- or emulsion polymerization techniques.
• the polymerisation can be a thermal or photochemical polymerisation.
• Useful free radical initiators include azo compounds, such as azo(bis)- isobutyronitrile and azo(bis)-2-cyanovaleric acid, hydroperoxides such as cumene, t-butyl and t-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl and dicumylperoxide, peroxyesters such as t-butylperbenzoate and di-t-butylperoxy phtalate, diacylperoxides such as benzoyl peroxide and lauroyl peroxide.
• azo compounds such as azo(bis)- isobutyronitrile and azo(bis)-2-cyanovaleric acid
• hydroperoxides such as cumene, t-butyl and t-amyl hydroperoxide
• dialkyl peroxides such as di-t-butyl and dicumylperoxide
• peroxyesters such as t-butyl
• the fluorochemical composition is soluble in various organic solvents such as ethyl acetate, ethers (di-propylene glycol mono methyl ether, tetrahydrofuran, ethylene glycol ethers), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), alcohols (methanol, ethanol, isopropyl alcohol, glycols), dimethylpyrrolidone and mixtures thereof.
• the fluorochemical composition can be used as a solution in an organic solvent or alternatively, an emulsion of the fluorochemical composition in water can be prepared according to well-known techniques.
• a solution of the fluorochemical composition in an organic solvent e.g.
• ethylacetate gradually can be added to a solution of an emulsifier in water with vigorous stirring.
• the thus obtained pre-mix may then be subjected to ultrasound treatment or high shear homogenization to obtain a milky to transparent emulsion of the fluorochemical composition in water.
• the organic solvent can then be removed e.g. by distillation under reduced pressure.
• the fluorochemical composition of this invention can be applied using conventional application methods but is preferably used as an aqueous emulsion. Alternatively, it can be used as a treatment composition in solvent.
• An aqueous emulsion will generally contain water, an amount of fluorochemical composition effective to provide repellent properties to a substrate treated therewith, and a surfactant in an amount effective to stabilize the emulsion.
• Water is preferably present in an amount of about 70 to 2000 parts by weight based on 100 parts by weight of the fluorochemical composition of the invention.
• the surfactant is preferably present in an amount of about 1 to 25 parts by weight, preferably about 2 to 10 parts by weight, based on 100 parts by weight of the fluorochemical composition.
• Conventional cationic, nonionic, anionic, and zwitterionic surfactants are suitable.
• the amount of the treating composition applied to a substrate in accordance with this invention is chosen to impart the desired stain release properties to the substrate surface.
• an amount of treating composition sufficient to provide about 0.01% to 5% by weight, preferably about 0.05% to 2% by weight, based on the weight of the substrate, of fluorochemical composition on the treated substrate is sufficient.
• the amount which is sufficient to impart desired stain release can be determined empirically and can be increased as necessary or desired.
• fluorochemical composition of the invention there may also be added other fluorinated products, polymers or auxiliary products such as starch, dextrin, casein, polyvinyl alcohols, cellulose and cellulose derivatives such as cellulose ethers, copolymers of (meth)acrylic acid and alkyl esters of (meth)acrylic acid, polyglycols such polyethylene glycols, sizing agents, materials to improve water and/or oil repellency, fire proofing or antistatic properties, buffering agents, fungicidal agents, optical bleaching agents, sequestering agents, mineral salts, surface-active agents, or swelling agents to promote penetration.
• polymers or auxiliary products such as starch, dextrin, casein, polyvinyl alcohols, cellulose and cellulose derivatives such as cellulose ethers, copolymers of (meth)acrylic acid and alkyl esters of (meth)acrylic acid, polyglycols such polyethylene glycols, sizing agents, materials to improve water
• auxiliary products for use in the fluorochemical composition include polyvinyl alcohols, polyethylene glycols, non-ionic cellulose ethers and copolymers of an alkyl (meth)acrylate and (meth)acrylic acid. It was found that in many cases, these auxiliary products improve the stain release performance of the fluorochemical composition.
• Preferred polyvinyl alcohols are polyvinyl alcohols having a degree of hydrolysis of at least about 65% by weight and more preferably a degree of hydrolysis of at least about 80% by weight.
• non-ionic cellulose ether derivatives include methyl cellulose, hydroxypropyl cellulose and methylhydroxypropyl cellulose.
• Particularly preferred cellulose ethers are hydroxyalkyl cellulose ethers.
• the etherified cellulose is highly hydrophilic. Accordingly, cellulose ethers that contain large hydrophobic substituents, such as the hydrophobically modified cellulose ether available from Aqualon under the trademark NEXTONTM, are not preferred for use in the fluorochemical composition of this invention.
• the polyethylene glycols useful as additives are preferably homopolymers of ethylene oxide and typically have a molecular weight between about 200 and 5000.
• Preferred copolymers of an alkyl(meth)acrylate and (meth)acrylic acid are copolymers in which the weight ratio of (meth)acrylic acid to the alkyl(meth)ac ⁇ ylate is between about 20:80 and 90: 10. More preferably, the weight ratio is between about 50:50 and 85: 15. It is further preferred that the alkyl group of the (meth)acrylate monomer is a lower alkyl group having about 1 to 6 carbon atoms. Examples of alkyl (meth)acrylate monomers include, methyl, ethyl and n- butyl acrylates and methacrylates.
• the copolymer of an alkyl (meth)acrylate and (meth)acrylic acid may further contain moieties derived from ethylenically unsaturated monomers, but preferably, the copolymer only consists of moieties derived from alkyl (meth)acrylates and (meth)acrylic acid.
• the copolymer may also be partially or fully neutralised with a base such as sodium hydroxide or ammonium hydroxide.
• the substrates treated with the fluorochemical composition of this invention are not especially limited and include plastic, metal, glass, fibrous materials such as textile fabrics, wood, non-wovens and paper.
• the fluorochemical composition is particularly useful for imparting stain release properties to a substrate that comprises natural fibers, in particular a substrate that consists of cellulose fibers or a substrate consisting of cellulose and polyester fibers.
• Substrates treated with a fluorochemical composition of this invention have particular good stain release properties for dirty motor oil stains and tea stains.
• the substrate can be immersed in a diluted emulsion.
• the saturated substrate can then be run through a padder/roller to remove excess emulsion, dried and cured in an oven at a temperature and for a time sufficient to provide a cured treated substrate.
• This curing process is typically carried out at temperatures between about 50°C to 190°C depending on the particular system or application method used. In general, a temperature of about 120°C to 170°C, preferably about 150°C to 170°C for a period of about 20 seconds to 10 minutes, preferably 3 to 5 minutes, is suitable.
• the cured treated substrate can be used as desired, e.g., incorporated or fashioned into a garment.
• Treatment baths were formulated containing a defined amount of the fluorochemical treatment agent. Treatments were applied to the test substrates by padding to provide a concentration of 0.3% or 0.6% solids (based on fabric weight and indicated as SOF (solids on fabric)) and drying the samples at 150°C during 3 minutes. Test substrates used in the Examples were based on polyester/cotton 67/33 blends (PES/CO), which were commercially available from Arlitex, Avelgem, Belgium. After drying, the substrates were tested for their stain release and repellency properties.
• PES/CO polyester/cotton 67/33 blends
• the stain release test was performed using two types of stains : - Dirty Motor Oil (DMO) obtained from General Motors Garage Houttequiet,
• Staining Procedure 2 Brush Method For this procedure, 0.35 ml DMO or 0.5 ml tea were placed on 10 cm xlO cm test samples. The stain was brushed into the fabric by brushing 3 times around in a plastic holder of 5 cm diameter placed around the staining liquid. The reflection measurement was done as described above.
• test samples were pinned on a PES/CO ballast of 3kg and laundered in a Miele washing machine type W 832.
• a commercial detergent (20 g kg Clax 100, available from Diversy Lever) was added and the substrates were washed at 70°C, using the main washing program, followed by four rinse cycles and centrifuging.
• the samples were dried in a tumble dryer and ironed at 150°C for 15 seconds. Unstained samples were treated the same way.
• the samples were measured with the Minolta meter and compared to unstained samples, resulting in a ⁇ L LD7 o ° c value.
• % ⁇ L ( ⁇ LrN - ⁇ LLD7O O C/ ⁇ L ⁇ N) x 100 gave an indication of the percentage of stain removed during the laundering process. The higher the value, the better the stain removal.
• the water repellency (WR) of a substrate was measured using a series of water-isopropyl alcohol test liquids and was expressed in terms of the "WR" rating of the treated substrate.
• the WR rating corresponded to the most penetrating test liquid which did not penetrate or wet the substrate surface after 15 seconds exposure. Substrates which were penetrated by or were resistant only to 100% water (0% isopropyl alcohol), the least penetrating test liquid, were given a rating of 0, whereas substrates resistant to a test liquid of 100% isopropyl alcohol (0% water), the most penetrating test liquid, were given a rating of 10.
• the oil repellency of a substrate was measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No. 118-1983, which test was based on the resistance of a treated substrate to penetration by oils of varying surface tensions. Treated substrates resistant only to Nujol® mineral oil (the least penetrating of the test oils) were given a rating of 1, whereas treated substrates resistant to heptane (the most penetrating of the test liquids) were given a rating of 8. Other intermediate values were determined by use of other pure oils or mixtures of oils, as shown in the following Table.
• PEG 200"8000 polyethyleneglycol, superscript number being indicative of the molecular weight (Mw), available from Huls, Germany
• PEG 350 -MA polyethyleneglycol methacrylate, superscript number being indicative of Mw, available from Inspec, Belgium
• MPEG 750 -A acrylate from polyethylene glycol methyl ether, superscript number being indicative of Mw, available from Inspec, Belgium
• MPEG 350"550 -MA polyethylene glycol methyl ether methacrylate, the superscript number being indicative of Mw, available from Inspec, Belgium
• PEG 468 - A Polyethylene glycol acrylate, the superscript number being indicative of Mw, available from Inspec, Belgium
• TEA triethylamine
• HOEMA 2-hydroxyethyl methacrylate
• GMA glycidyl methacrylate (2,3-epoxypropyl methacrylate)
• IPDI isophorone diisocyanate
• Arquad T-50 tallow trimethyl ammonium chloride, available from Akzo,
• PNA polyvinyl alcohol
• MowiolTM polyvinyl alcohol available from Hoechst, with various weight average molecular weights and degree of hydrolysis as indicated in the table:
• PolyviolTM N03/180 polyvinyl alcohol, with a degree of hydrolysis of 82, viscosity (Hoppler) of a 4% solution in water at 20°C in mPas of 3 +/- 0.5, available from Wacker-Chemie.
• PolyviolTM W25/190 polyvinyl alcohol with a degree of hydrolysis of 81, and viscosity (Hoppler) of a 4% solution in water at 20°C in mPas of 25 +/- 1.5, available from Wacker-Chemie.
• BA n-butylacrylate
• MAA methacrylic acid ⁇ aOH : sodium hydroxide
• MAP 1 (meth)acrylic polymer BA/MAA 18.6/81.4, prepared according to the following procedure :
• a polymerization flask was charged with 12.5 g methacrylic acid, 37.5 g butylacrylate and 1 g sulphated castor oil. After addition of 200 g water and 30 g acetone, the reaction mixture was degassed using nitrogen. 0.5 g
• CulminalTM CulminalTM MHPC 50, a methylhydroxypropyl cellulose available from
• the fluorochemical urethane acrylate monomers (FM) listed in Table 2 were prepared according to the general procedure as described below.
• HFO Hydroxy terminated fluorochemical oligomers
• a round bottom flask equipped with two reflux condensors, a stirrer, a temperature control, a nitrogen inlet and a vacuo outlet was charged with 2.4 moles MEFOSEA and 987 g EtOAc.
• the mixture was heated at 40°C until all fluorochemical monomer was dissolved.
• 0.6 moles 2-mercaptoethanol and 0.15% AIBN were added.
• the reaction mixture was gradually heated to 80°C.
• the reaction was run under nitrogen atmosphere at 80°C for 16 hours, after which more than 95% conversion was obtained.
• Fluorochemical urethane acrylate monomers not comprising a polyoxyalkylene chain were made using a procedure similar to the synthesis of HOEMA/LPDI/HFO-1 in equimolar ratio (FM-10, Table 2) which is hereafter described.
• a round bottom flask equipped with a condensor, a mechanical stirrer and a temperature control was charged with 100.9 g HFO-1, 8.9 g IPDI, 173 g EtOAc, 5.21 g HOEMA and 0.06 g MEHQ.
• the reaction mixture was heated at 65°C until all chemicals were dissolved. 4 drops stannous octanoate were added and the reaction was run at 75°C for 16 hours.
• composition of the polymers prepared under step C is given in Table 3.
• the optimal amount of fluorochemical compound needed to treat the substrate depends on the particular fluorochemical composition used. It can further be seen that not only was good stain release obtained, but all treated PES/CO substrates show remarkable high oil and especially high water repellencies, indicating that the compositions are suitable for use as fluorochemical repellent agents. This is a further advantage over the untreated samples which show no oil or water repellency at all.
• Example 26 to 54 the same type of experiment was repeated but this time the DMO was applied to the fabric by the brush method. Comparative Example C-2 was made with untreated PES/CO substrate. The results of stain release and oil and water repellency are given in Table 5.
• Example 71 to 103 treated PES/CO substrates were tested with tea stains, but now using the brush method. Comparative Example C-4 was made with untreated PES/CO substrate. The results of stain release and oil and water repellency are given in Table 7.
• Example 104 to 111 PES/CO substrate was treated with fluorochemical compound FC-37 (Example 104) or with a 50/50 blend of FC-37 with various polyvinyl alcohols as reported in Table 8 (Examples 105 to 111).
• the substrate was treated in such a way as to have 0.6% SOF fluorochemical compound and 0.6% SOF polyvinyl alcohol (except Example 104).
• Comparative Example C-5 was made using untreated PES/CO.
• the treated and untreated substrates were stained with DMO (brush) and tested for their stain release and repellency properties. The results are given in Table 8.
• PES/CO substrate was treated with fluorochemical compounds FC-17 and FC-35 or with a 50/50 blend of the fluorochemical compound and polyvinyl alcohol MowiolTM 3-83.
• the substrate was treated in such a way as to have 0.6% fluorochemical compound and 0.6% SOF polyvinyl alcohol.
• the treated substrates were stained with Tea or DMO (brush) and tested for their stain release and oil and water repellency properties. The results are reported in Table 9.
• Examples 120 to 129 and Comparative Examples C-6 and C-7 PES/CO substrate was treated with fluorochemical compound FC-37 or with a 50/50 blend of FC-37 with polyvinyl alcohol, as shown in Table 10. The substrate was treated in such a way as to have 0.6% SOF fluorochemical compound or 0.6% SOF fluorochemical compound and 0.6% SOF polyvinyl alcohol. Comparative Examples C-6 and C-7 were made using untreated PES/CO. The treated and untreated substrates were stained with tea or wine and tested for their stain release and repellency properties. The results are reported in Table 10.
• the addition of polyvinyl alcohol to the fluorochemical composition also slightly improves the stain release performance of the composition relative to aqueous based stains.
• PES/CO substrate was treated with fluorochemical compounds FC-17, FC-35 or FC-37 or with a 50/50 blend of the fluorochemical compound with CulminalTM MHPC 50 or KlucelTM M, as given in Table 11.
• the substrate was treated in such a way as to have 0.6% SOF fluorochemical compound or 0.6% SOF fluorochemical compound and 0.6% SOF Cellulose derivative.
• the treated substrates were stained with tea or DMO (brush) and tested for their stain release and repellency properties. The results are given in Table 11.
• Examples 130 to 147 show that the stain release properties can also be improved by using a non-ionic cellulose ether in the fluorochemical composition.
• Examples 148 to 167 show that the stain release properties can also be improved by using a non-ionic cellulose ether in the fluorochemical composition.
• PES/CO substrate was treated with fluorochemical compounds FC-17, FC-35 or FC-37 or with a 50/50 blend of the fluorochemical compound with (meth)acrylic polymers as shown in Table 12.
• the substrate was treated in such a way as to have 0.6% SOF fluorochemical compound or 0.6% SOF fluorochemical compound and 0.6% SOF (meth)acrylic polymer.
• the treated substrates were stained with tea or DMO and tested for their stain release and repellency properties (brush method). The results are shown in Table 12.
• stain release could be improved by adding a copolymer of an alkyl (meth)acrylate and (meth)acrylic acid to the fluorochemical composition.
• PES/CO substrate was treated with fluorochemical compounds FC-17, FC-35 or FC-37 or with a 50/50 blend of the fluorochemical compound with polyethyleneglycol of various molecular weight, as given in Table 13.
• the fluorochemical compound and the polyethyleneglycol (when used) were applied at 0.6% SOF each.
• the treated substrates were stained with DMO or tea and tested for their stain release properties (brush method). The results are shown in Table 13.

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